CN100519925C - Polyurethane synthetic leather grain surface paste and method for preparing same - Google Patents
Polyurethane synthetic leather grain surface paste and method for preparing same Download PDFInfo
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- CN100519925C CN100519925C CNB2006101545326A CN200610154532A CN100519925C CN 100519925 C CN100519925 C CN 100519925C CN B2006101545326 A CNB2006101545326 A CN B2006101545326A CN 200610154532 A CN200610154532 A CN 200610154532A CN 100519925 C CN100519925 C CN 100519925C
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Abstract
The polyurethane artificial leather pellet paste features in adding chrome leather into polyurethane resin with the chrome leather embedding into the polyurethane molecular chain, forming a new kind of artificial leather pellet paste, with the produced artificial leather having 400- 700g/m2/24h water vapor permeability, possessing the features of absorption of moisture, permeability to air and good tactility, improving the simulation property of the artificial leather with the quality close to the natural leather.
Description
(1) technical field
The present invention relates to be used to prepare polyurethane synthetic leather grain surface paste and preparation method thereof.
(2) background technology
The PU synthetic leather is the macromolecular material of imitation natural leather internal structure and application performance, normally the perforated nonwoven fabrics with dipping is a lamina reticularis, the microvoid polyurethane resin is a grain layer, its outward appearance is all similar to natural leather with internal structure, elasticity is moderate, having certain percentage elongation and gas permeability, is the optimal substitute material of natural leather.But some performance of Synthetic Leather still is unable to catch up with natural leather far away, as the waterproofing and moisture-penetration performances and the comfort of natural leather, with the footwear that Synthetic Leather is made, can not absorb and get rid of the sweat that pin produces, and it is uncomfortable that feel is felt.Increase substantially the Synthetic Leather properties of product, make it more near natural leather, the performance of polyurethane synthetic leather grain surface paste is crucial.Grain surface paste is major ingredient with the polyurethane resin.Polyurethane resin itself easily forms fine and close rete, makes a synthetic emulation skin decreased performance.In order to improve the problems referred to above, people have carried out a large amount of work, as utilize solvent effusion pore-creating on the polyurethane synthetic leather grain surface layer, use other synthetic resin modified polyurethane resin or the like, though these methods make moderate progress the performance of synthetic leather, comparing with natural leather differs greatly (can reach 800g/m as the poisture-penetrability of natural leather
2About 24h, the polyurethane wet-method synthetic leather can only reach 400g/m
224h), the quality of synthetic leather improves few.
(3) summary of the invention
The object of the invention provides a kind of new polyurethane synthetic leather grain surface paste, can make performance more near the Synthetic Leather of natural leather with grain surface paste of the present invention, makes the Synthetic Leather of making have higher sanitation performance.In order to realize the object of the invention, technical scheme of the present invention is as follows:
A kind of polyurethane synthetic leather grain surface paste, comprise polyester polyol, solvent dimethylformamide (DMF), dihydroxylic alcohols (diglycol), 4 in the slurry, 4 '-methyl diphenylene diisocyanate (MDI), anion surfactant, non-ionic surface active agent, also have the chrome tanning leather in the slurry, specifically polyurethane synthetic leather grain surface paste is made up of the following component of quality percentage composition:
Siccative chrome tanning leather 2-15%
Molecular weight is 2000 polyester polyol 5-10%
Dimethyl formamide 45-80%
Diglycol 2-8%
4,4 '-methyl diphenylene diisocyanate 5-26%
Anion surfactant 0.5-1%
Non-ionic surface active agent 0.5-1%.
Described siccative chrome tanning leather is for taking off chromium chrome tanning leather through what take off that chromium handles.Molecular weight is that 2000 polyester polyol can replace with molecular weight 1000～2000 polyester polyol, but its mass content should be that the mol ratio of 2000 polyester polyol and reactant is recast according to above-mentioned molecular weight.
The optimization polyurethane synthetic leather grain surface paste is made up of the following component of quality percentage composition:
Siccative chrome tanning leather 2-15%
Molecular weight is 2000 polyester polyol 5-10%
Dimethyl formamide 60-80%
Diglycol 2-8%
4,4 '-methyl diphenylene diisocyanate 5-15%
Anion surfactant 0.5-1%
Non-ionic surface active agent 0.5-1%.
Main invention main points of the present invention are the chrome tanning leather to be joined in the use for synthetic leather polyurethane resin go, and the chrome tanning leather is embedded in the polyurethane molecular chain, form new synthetic leather grain surface paste, and this can improve the performance of use for synthetic leather polyurethane resin.
One of described anion surfactant recommendation use is following: with dioctyl maleate sodium sulfonate, bleeding agent SF-11 (Jiande City Shunfa Chemical Additive Co., Ltd.), bleeding agent LA-104 (Shanghai Tiantan Accessory Ingredient Co., Ltd); More preferably dioctyl maleate sodium sulfonate (OT-70).One of described non-ionic surface active agent recommendation use is following: sorbitan mono-oleic acid ester, octadecanol; More preferably sorbitan mono-oleic acid ester (S-80).
Described polyurethane synthetic leather grain surface paste is recommended to be made up of the following component of quality percentage composition:
Siccative takes off chromium chrome tanning leather 6%
Molecular weight is 2000 polyester polyol 8%
Dimethyl formamide 700%
Diglycol 30%
4,4 '-methyl diphenylene diisocyanate 11%
Dioctyl maleate sodium sulfonate 1%
Sorbitan mono-oleic acid ester 1%.
Above-mentioned siccative takes off the method for making of chromium chrome tanning leather for the chrome tanning leather is ground into onal, place concentration 5～15% hexanedioic acids and oxalic acid (W/W is 1:1) mixed aqueous solution in 48～52 ℃, temperature was soaked 5～20 hours, ultrasonic wave took off chromium 2～4 hours, chrome liquor is taken off in elimination, filter cake spend deionised water to the pH of washing lotion for neutral, be dried into material and take off chromium chrome tanning leather.
The preparation method of polyurethane synthetic leather grain surface paste of the present invention takes by weighing each component by following prescription, siccative chrome tanning leather 2-15% earlier; Molecular weight is 2000 polyester polyol 5-10%; Dimethyl formamide 60-80%; Diglycol 2-8%; 4,4 '-methyl diphenylene diisocyanate 5-15%; Anion surfactant 0.5-1%; Non-ionic surface active agent 0.5-1%; Preparation as follows again:
(1) gives and earlier siccative chrome tanning leather is made particle, in reactor, add the dimethyl formamide that is enough to make the submergence of prescription amount chrome tanning leather particle, add chrome tanning leather particle again and flood to dissolve fully and make chrome tanning leather solution to chrome tanning leather fragment;
(2) preparation slurry: with the polyester polyol dimethyl formamide of prescription amount is in the solvent adding reactor, dimethyl formamide for the submergence polyester polyol for well.Be warming up to 50～60 ℃, stirring is dissolved polyester polyol fully, add 4 of prescription amount more in batches, 4 '-methyl diphenylene diisocyanate, diglycol and step (1) make chrome tanning leather solution, while is along with the increase of reaction mass viscosity, it is 25～35% that the adding dimethyl formamide makes the slurry solid content, diluting reaction 7～20 hours, here along with the increase of reaction mass viscosity, the main purpose that adds dimethyl formamide is to make slurry keep certain viscosity, adds non-ionic surface active agent again, anion surfactant, constant temperature stirs, and discharging obtains polyurethane synthetic leather grain surface paste.Temperature in the described preparation process in the reactor is advisable to be no more than 60 ℃.
The method of polyurethane synthetic leather grain surface paste of the present invention, preferred chrome tanning leather is for taking off chromium chrome tanning leather, described processing method of taking off chromium chrome tanning leather is: the chrome tanning leather is ground into onal, the submergence in the mixed aqueous solution of the hexanedioic acid of concentration 10% and oxalic acid (the quality proportioning is 1:1) of described onal, be incubated 8 hours down at 40～50 ℃, took off chromium 3 hours with ultrasonic wave again, 40～50 ℃ of temperature, power that ultrasonic wave takes off chromium are 20～100W.Chrome liquor is taken off in elimination, filter cake spend deionised water to the pH of washing lotion for neutral, oven dry, stand-by.
Described ultrasonic wave takes off preferred 45 ℃ of chromium temperature, power 77W.Concrete described method is by 1000 kilograms of polyurethane synthetic leather grain surface pastes of preparation, and preparation process is as follows:
A, the chrome tanning leather is taken off chromium, washing, oven dry handle, get 60 kilograms of chrome tanning leathers, be ground into 2mm
2Onal, throw onal in 60 kilograms of concentration 10% mass ratioes: in the hexanedioic acid of 1:1 and the oxalic acid mixed solution, in 45 ℃ of heating 8 hours, ultrasonic power 77W took off chromium 3 hours, and chrome liquor is taken off in elimination, spend deionised water to the pH of washing lotion for neutral, oven dry is made and is taken off chromium chrome tanning leather fragment;
B, (1) is in 54 kilograms of reactors of packing into of dimethyl formamide, takes off the chromium chrome tanning leather fragment reactor of packing into after will handling then, floods to make the dissolving of chrome tanning leather fragment in 2 hours, obtains taking off 400 kilograms of chromium chrome tanning leather mixed solutions, and is standby.
(2) preparation slurry: in 80 kilograms of polyester polyol, 200 kilograms of adding reactors of dimethyl formamide, heat up 55 ℃, after being stirred to dissolving fully, add 4 of prescription amount in batches, 4 '-methyl diphenylene diisocyanate, diglycol and step (1) make 400 kilograms of chrome tanning leather solution, along with the increase of reaction mass viscosity, the temperature that adds 160 kilograms of dimethyl formamide dilution maintenance reactors can not be above 60 ℃; Reaction continues 14～16 hours, adds 10 kilograms of dioctyl maleate sodium sulfonates, 10 kilograms of sorbitan mono-oleic acid esters again, and constant temperature stirred 20～40 minutes, and discharging obtains 1000 kilograms of polyurethane synthetic leather grain surface pastes.
Leather after will pulverizing in the production process of the present invention takes off chromium, washing, oven dry, and dimethyl formamide (DMF) mixed solution that is mixed with 10%-15% again is standby.Leather collagen fiber molecular separating force after the processing reduces, and activated group is exposed outside, and the leather molecule is activated.Leather molecule with activation is incorporated in the strand of polyurethane resin the polyurethane resin performance improvement then.Polyurethane resin with modification is that major ingredient is produced the Synthetic Leather grain surface paste, can produce a kind of novel synthetic leather.
The present invention compared with prior art earlier produces performed polymer with polyester polyol and MDI reaction, and use is taken off chromium chrome tanning leather and carried out chain extension then, makes the polyurethane molecular chain obtain modification, obtains novel polyurethane synthetic leather grain surface paste.Its beneficial effect is embodied in: the synthetic leather poisture-penetrability of using the present invention to produce generally can reach 400-700g/m
224h has the characteristic of moisture absorption, ventilative, good hand feeling, has improved the synthetic leather simulation performance, has improved the class of synthetic leather, makes synthesising leather performance more near natural leather.
(4) specific embodiment
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Embodiment 1
Per 1000 kilograms of slurries are made up of the following component of content:
Siccative takes off chromium chrome tanning leather 60kg
Molecular weight is 2000 polyester polyol 80kg
Dimethyl formamide 700kg
Diglycol 30kg
4,4 '-methyl diphenylene diisocyanate 110kg
Dioctyl maleate sodium sulfonate 10kg
Sorbitan mono-oleic acid ester 10kg
The first step is taken off chromium, washing, oven dry processing to the chrome tanning leather.Get 60 kilograms of chrome tanning leathers, be ground into 2mm
2About onal, throw onal in 60 kilograms of concentration 10% hexanedioic acids and oxalic acid (mass ratio: 1:1), 45 ℃ of heating 8 hours, ultrasonic wave took off chromium 3 hours, filter and take off chrome liquor, and the pH that uses deionized water to wash washing lotion is about 7, oven dry, 55 kilograms of siccatives to take off chromium chrome tanning leather stand-by.
Dimethyl formamide (DMF) 345 kilograms (for the first time) is packed in the reactor, the reactor of packing into of the chrome tanning leather particle after will handling then, after 2 hours, chrome tanning leather fragment is dissolved among the DMF fully, and it is standby to obtain 400 kilograms of storages of chromed tanned leather liquid.
Second step, the preparation slurry.80 kilograms of polyester polyol (molecular weight 2000), dimethyl formamide (DMF) 200 kilograms (for the second time) are added in the reactor, heat up 55 ℃, after being stirred to dissolving fully, add 4 in batches, behind 110 kilograms of 4 '-methyl diphenylene diisocyanates (MDI), add 30 kilograms of diglycols, add 400 kilograms of chrome tanning leather solution again, increase along with reaction mass viscosity, add DMF dilution (adding the DMF155 kilogram again) (for the third time), making the slurry solid content is 30%, and the temperature of attentive response still can not be above 60 ℃.Begin to finish to need 15 hours altogether from adding MDI to reaction.Add surfactant, anion surfactant adopts dioctyl maleate sodium sulfonate (OT-70) 10 kilograms, and non-ionic surface active agent adopts sorbitan mono-oleic acid ester (S-80) 10 kilograms, and constant temperature stirred 30 minutes, discharging obtains 1000 kilograms of polyurethane synthetic leather grain surface pastes.
The solid content of the polyurethane synthetic leather grain surface paste of the present embodiment preparation: 30%; Viscosity (25 ℃): 7500mPas; Gelation rate: 15min.
Embodiment 2
Produce 1000 kilograms of slurries by embodiment 1 and carry out prescription.
The first step: by the method for embodiment 1 60 kilograms of chrome tanning leathers are taken off chromium, washing, oven dry and handle the siccative of getting the prescription amount and take off chromium chrome tanning leather.
And by embodiment 1 first step method: dimethyl formamide (DMF) 345 kilograms (for the first time) is packed in the reactor, chrome tanning leather particle after will handling the then reactor of packing into, after 2 hours, chrome tanning leather fragment is dissolved among the DMF fully, and it is standby to obtain 400 kilograms of storages of chromed tanned leather liquid.
Second step: get dimethyl formamide 200 kilograms (for the second time) and drop in the reactor, add polyester polyol (molecular weight 2000) 80 kilograms, 30 kilograms of diglycols, elevated temperature to 60 ℃, after treating material dissolution, add 4,110 kilograms of 4 '-methyl diphenylene diisocyanates, react after 3 hours, add 400 kilograms of chromed tanned leather liquid.Temperature constant is at 60 ℃, and progressively adds DMF and carry out the viscosity adjustment along with viscosity raises, and adds 255 kilograms of dimethyl formamides (for the third time) again.This process was carried out about 13 hours.Be sequentially added into 10 kilograms of 10 kilograms of SF-11 and sorbitan mono-oleic acid esters (S-80).Continue to stir after 2 hours, go out still and obtain 1000 kilograms in slurry.
The solid content of the polyurethane synthetic leather grain surface paste of the present embodiment preparation: 30%; Viscosity (25 ℃): 7500mPas; Gelation rate: 15min.
Embodiment 1 difference from Example 2 be the feeding sequence difference of diglycol, and the feeding sequence of other material is constant.
Embodiment 3～8
Embodiment 3～8 feeds intake by table 1, is made up of the following component of content with per 1000 kilograms of slurries, and example 3～5 technical process are identical with embodiment 1, and example 6～8 technical process are identical with embodiment 2:
Table 1
Parameters such as table 2 with the polyurethane synthetic leather grain surface paste of the pulp preparation of embodiment 3～8
| Embodiment | Solid content/% | Viscosity (25 ℃)/mPas ℃ | Gelation rate/min |
| 3 | 21 | 2500 | 25 |
| 4 | 47 | 10000 | 10 |
| 5 | 42 | 9500 | 11 |
| 6 | 42 | 9500 | 11 |
| 7 | 40 | 9000 | 13 |
| 8 | 52 | 12500 | 9 |
Claims (10)
1. polyurethane synthetic leather grain surface paste is characterized in that described slurry is made up of the following component of quality percentage composition:
Siccative chrome tanning leather 2-15%
Molecular weight is 2000 polyester polyol 5-10%
Dimethyl formamide 45-80%
Diglycol 2-8%
4,4 '-methyl diphenylene diisocyanate 5-26%
Anion surfactant 0.5-1%
Non-ionic surface active agent 0.5-1%.
2. polyurethane synthetic leather grain surface paste as claimed in claim 1 is characterized in that using the chromium chrome tanning leather that takes off through taking off the chromium processing to replace siccative chrome tanning leather.
3. polyurethane synthetic leather grain surface paste as claimed in claim 1 or 2 is characterized in that described anion surfactant is one of following: dioctyl maleate sodium sulfonate, bleeding agent SF-11, bleeding agent LA-104.
4. polyurethane synthetic leather grain surface paste as claimed in claim 1 or 2 is characterized in that described non-ionic surface active agent is one of following: sorbitan mono-oleic acid ester, octadecanol.
5. polyurethane synthetic leather grain surface paste is characterized in that described slurry is made up of the following component of quality percentage composition:
Siccative takes off chromium chrome tanning leather 6%
Molecular weight is 2000 polyester polyol 8%
Dimethyl formamide 70%
Diglycol 3%
4,4 '-methyl diphenylene diisocyanate 11%
Dioctyl maleate sodium sulfonate 1%
Sorbitan mono-oleic acid ester 1%.
6. polyurethane synthetic leather grain surface paste as claimed in claim 5, it is characterized in that described siccative takes off the method for making of chromium chrome tanning leather for siccative chrome tanning leather is ground into onal, the quality proportioning that places concentration 5～15% is that the hexanedioic acid of 1:1 and oxalic acid mixed aqueous solution are in 48～52 ℃, temperature was soaked 5～20 hours, ultrasonic wave took off chromium 2～4 hours, chrome liquor is taken off in elimination, filter cake spend deionised water to the pH of washing lotion for neutral, be dried into siccative and take off chromium chrome tanning leather.
7. method for preparing polyurethane synthetic leather grain surface paste as claimed in claim 1 is characterized in that described slurry is made up of the following component of quality percentage composition:
Siccative chrome tanning leather 2-15%
Molecular weight is 2000 polyester polyol 5-10%
Dimethyl formamide 45-80%
Diglycol 2-8%
4,4 '-methyl diphenylene diisocyanate 5-26%
Anion surfactant 0.5-1%
Non-ionic surface active agent 0.5-1%
Described method comprises the steps:
(1) in advance siccative chrome tanning leather is made onal, in reactor, add the dimethyl formamide be enough to make the submergence of prescription amount siccative chrome tanning leather onal, add siccative chrome tanning leather onal again and flood to dissolve fully and make chrome tanning leather solution to siccative chrome tanning leather onal;
(2) preparation slurry: with the molecular weight of prescription amount is that 2000 polyester polyol dimethyl formamides are that solvent adds in the reactor, it is 2000 polyester polyol that described dimethyl formamide addition is answered the submergence molecular weight, be warming up to 50～60 ℃, it is that 2000 polyester polyol are dissolved fully that stirring makes molecular weight, add 4 of prescription amount more in batches, 4 '-methyl diphenylene diisocyanate, diglycol and step (1) make chrome tanning leather solution, while is along with the increase of reaction mass viscosity, adding dimethyl formamide again, to make the slurry solid content be 25～35%, diluting reaction 7～20 hours; Add non-ionic surface active agent again, anion surfactant, constant temperature stirs, and discharging obtains polyurethane synthetic leather grain surface paste.
8. the method for polyurethane synthetic leather grain surface paste as claimed in claim 7, it is characterized in that replacing siccative chrome tanning leather with taking off chromium chrome tanning leather, described processing method of taking off chromium chrome tanning leather is: siccative chrome tanning leather is ground into onal, described onal is submergence in the hexanedioic acid of 1:1 and the oxalic acid mixed aqueous solution in the quality proportioning of concentration 10%, be incubated 8 hours down at 40～50 ℃, took off chromium 3 hours with ultrasonic wave again, its ultrasonic power is 20～100W, temperature is 40～50 ℃, chrome liquor is taken off in elimination, filter cake spend deionised water to the pH of washing lotion for neutral, oven dry, stand-by.
9. the method for polyurethane synthetic leather grain surface paste as claimed in claim 8 is characterized in that the ultrasonic power when described ultrasonic wave takes off chromium is 77W, and temperature is 45 ℃.
10. the method for polyurethane synthetic leather grain surface paste as claimed in claim 8 is characterized in that described method by 1000 kilograms of polyurethane synthetic leather grain surface pastes of preparation, and preparation process is as follows:
A, siccative chrome tanning leather is taken off chromium, washing, oven dry handle, get 60 kilograms of siccative chrome tanning leathers, be ground into 2mm
2Onal, throw onal in 60 kilograms of concentration 10% mass ratioes: in the hexanedioic acid of 1:1 and the oxalic acid mixed solution, in 45 ℃ of heating 8 hours, power is that the ultrasonic wave of 77W took off chromium 3 hours, chrome liquor is taken off in elimination, spend deionised water to the pH of washing lotion for neutral, oven dry is made and is taken off chromium chrome tanning leather onal;
B, (1) is in 345 kilograms of reactors of packing into of dimethyl formamide, takes off the chromium chrome tanning leather onal reactor of packing into after will handling then, floods to make in 2 hours and takes off the dissolving of chromium chrome tanning leather onal, obtains taking off 400 kilograms of chromium chrome tanning leather mixed solutions, and is standby;
(2) preparation slurry: is molecular weight in 80 kilograms of 2000 polyester polyol, 200 kilograms of adding reactors of dimethyl formamide, heat up 55 ℃, after being stirred to dissolving fully, add 4 in batches, 110 kilograms of 4 '-methyl diphenylene diisocyanates, 30 kilograms of diglycols and step (1) make takes off 400 kilograms of chromium chrome tanning leather mixed solutions, along with the increase of reaction mass viscosity, the temperature that adds 155 kilograms of dimethyl formamide dilution maintenance reactors can not be above 60 ℃; Reaction continues 14～16 hours, adds 10 kilograms of dioctyl maleate sodium sulfonates, 10 kilograms of sorbitan mono-oleic acid esters again, and constant temperature stirred 20～40 minutes, and discharging obtains 1000 kilograms of polyurethane synthetic leather grain surface pastes.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101338016B (en) * | 2007-07-04 | 2010-12-08 | 上海华峰超纤材料股份有限公司 | High springback wet method polyurethane resin for superfine fiber chemical leather |
| CN100570049C (en) * | 2007-10-12 | 2009-12-16 | 华伦皮塑（苏州）有限公司 | A kind of preparation method of synthetic leather dry process PU slurry |
| CN102443184B (en) * | 2011-09-26 | 2013-04-10 | 陕西科技大学 | Preparation method of surface reactive collagen fiber/polyester composite material |
| CN108951178A (en) * | 2017-05-23 | 2018-12-07 | 天守(福建)超纤科技股份有限公司 | Resin microfiber synthetic leather and preparation method thereof can be breathed |
| CN108103798B (en) * | 2018-01-23 | 2020-09-01 | 陕西科技大学 | High-cold-resistance automobile superfine fiber synthetic leather and production method thereof |
| CN112341591B (en) * | 2020-10-27 | 2023-03-24 | 上海伊纯实业有限公司 | Polyurethane material and preparation method and application thereof |
| CN113622190B (en) * | 2021-08-06 | 2023-05-23 | 武汉纺织大学 | Garment imitation leather color functional yarn and preparation method thereof |
| CN113801286B (en) * | 2021-09-03 | 2022-07-08 | 华南农业大学 | Modified anionic vegetable oil-based waterborne polyurethane emulsion and preparation method and application thereof |
| CN114232355A (en) * | 2021-12-22 | 2022-03-25 | 山东同大海岛新材料股份有限公司 | Preparation method of superfine fiber synthetic leather and superfine fiber synthetic leather |
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Assignee: Jiaxing Heda Technology Chemical Co., Ltd. Assignor: Wenzhou University Contract fulfillment period: 2009.9.3 to 2017.9.2 contract change Contract record no.: 2009330002534 Denomination of invention: Polyurethane synthetic leather grain surface paste and method for preparing same Granted publication date: 20090729 License type: Exclusive license Record date: 20091019 |
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